U.S. patent number 4,830,939 [Application Number 07/173,385] was granted by the patent office on 1989-05-16 for radiation cured solid electrolytes and electrochemical devices employing the same.
This patent grant is currently assigned to MHB Joint Venture. Invention is credited to Mei-Tsu Lee, Gerhart Schwab, Dale R. Shackle.
United States Patent |
4,830,939 |
Lee , et al. |
May 16, 1989 |
**Please see images for:
( Reexamination Certificate ) ** |
Radiation cured solid electrolytes and electrochemical devices
employing the same
Abstract
A method for forming an interpenetrating polymeric network
containing a liquid electrolyte for use in solid state
electrochemical cells which comprises forming a mixture of a liquid
monomeric or prepolymeric radiation polymerizable, compound, a
radiation inert ionically conducting liquid, and an ionizable
alkaline metal salt; subjecting said mixture to actinic radiation
to thereby crosslink said radiation polymerizable ionically
conducting material and form a solid matrix containing said
ionically conducting liquid; and electrode half elements and
electrochemical cells incorporating said network.
Inventors: |
Lee; Mei-Tsu (Centerville,
OH), Shackle; Dale R. (Springboro, OH), Schwab;
Gerhart (Chillicothe, OH) |
Assignee: |
MHB Joint Venture (Dayton,
OH)
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Family
ID: |
22361759 |
Appl.
No.: |
07/173,385 |
Filed: |
March 25, 1988 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
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115492 |
Oct 30, 1987 |
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Current U.S.
Class: |
429/312; 522/79;
522/96; 522/170; 522/81; 522/142; 429/314; 429/338 |
Current CPC
Class: |
C08F
299/022 (20130101); H01M 6/181 (20130101) |
Current International
Class: |
H01M
6/18 (20060101); H01M 6/18 (20060101); H01M
006/18 () |
Field of
Search: |
;429/192,194 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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0145498 |
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Jun 1985 |
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EP |
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0075779 |
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May 1983 |
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JP |
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Other References
"Conductivities of Solid Polymer Electrolyte Complexes of Alkali
Salts with Polymers of Methoxypolyethyleneglycol Methacrylates"
Solid State Ionics 14 (1984) 221-224 by Du Wei Xia et al..
|
Primary Examiner: Walton; Donald L.
Attorney, Agent or Firm: Smith & Schnacke
Parent Case Text
CROSS-REFERENCE TO RELATED APPLICATION
This application is a continuation-in-part of U.S. application Ser.
No. 115,492, filed Oct. 30, 1987 now abandoned.
Claims
What is claimed is:
1. A method for forming a polymeric network containing a liquid
electrolyte for use in solid state electrochemical cells which
comprises forming a mixture of a liquid, monomeric or prepolymeric,
radiation polymerizable, polyethylenically unsaturated compound, a
radiation inert ionically conducting liquid, and an ionizable
alkali metal salt, and subjecting said mixture to actinic radiation
to thereby crosslink said radiation polymerizable material and form
a solid matrix containing said ionically conducting liquid, said
ionically conducting liquid being an aprotic polar solvent.
2. The method of claim 1 wherein said radiation polymerizable
compound is a polyethylenically unsaturated compound including at
least one heteroatom in the molecule.
3. The method of claim 2 wherein said radiation polymerizable
compound includes a repeating unit selected from the group
consisting of ##STR2## where R.sup.1 is hydrogen or a lower alkyl
group.
4. The method of claim 3 wherein said radiation polymerizable
compound is represented by the formulas I to III below, ##STR3##
where n is about 3 to 50 and R is hydrogen or a C1-C3 alkyl group
and A represents an ethylenically unsaturated moiety or a glycidyl
moiety.
5. The method of claim 4 wherein said actinic radiation is
ultraviolet radiation or electron beam radiation.
6. The method of claim 2 wherein said radiation polymerizable
compound is a polyethylene glycol modified to include terminal
ethylenically unsaturated groups.
7. The method of claim 6 wherein said salt is a salt of a cation
selected from the group consisting of lithium, sodium, potassium,
and ammonium cations; and an anion selected from the group
consisting of I-, Br-, SCN- ClO.sub.4 -, CF.sub.3 SO.sub.3 -,
BF.sub.4 -, PF.sub.6 -, AsF.sub.6 -, and CF.sub.3 COO-.
8. The method of claim 7 wherein said radiation polymerizable
compound is polyethylene glycol diacrylate, polyethylene glycol
dimethacrylate, an acrylate functionalized polyurethane, or
polyethylene glycol diglycidyl ether.
9. The method of claim 7 wherein said ionically conducting liquid
is polyethylene glycol dimethyl ether.
10. The method of claim 7 wherein said radiation inert ionically
conducting liquid is present in said mixture in an amount of at
least 45% by weight.
11. The method of claim 10 wherein said radiation inert ionically
conducting liquid is present in said mixture in an amount of at
least 70% by weight.
12. The method of claim 11 wherein said liquid aprotic polar
solvent includes heteroatoms capable of forming donor acceptor
bonds with alkali metal cations.
13. The method of claim 12 wherein said aprotic polar solvent is
selected from the group consisting of propylene carbonate,
gamma-butyrolactone, 1,3-dioxolane, and
2-methyltetrahydrofuran.
14. The method of claim 7 wherein said radiation polymerizable
compound is a mixture of a difunctional and a trifunctional
polyethylenically unsaturated compound.
15. A solid state electrochemical cell including a polymeric
network formed by the method of claim 7 as an electrolyte.
16. The method of claim 1 wherein said liquid aprotic polar solvent
includes heteroatoms capable of forming donor acceptor bonds with
alkali metal cations.
17. A method for forming an anode half element which comprises
coating an anodic metal foil with a mixture which includes a
liquid, monomeric or prepolymeric radiation polymerizable,
polyethylenically unsaturated compound, a radiation inert ionically
conducting liquid, said ionically conducting liquid being an
aprotic polar solvent, and an ionizable alkali metal salt; and
subjecting said mixture to actinic radiation to thereby polymerize
said radiation polymerizable compound and form a solid matrix
containing said ionically conducting liquid.
18. The method of claim 17 wherein said radiation polymerizable
material is ionically conductive.
19. The method of claim 18 wherein said radiation polymerizable
compound is a polyethylenically unsaturated compound including at
least one heteroatom in the molecule.
20. The method of claim 19 wherein said anodic metal foil is a
lithium foil or a lithium coated foil.
21. The method of claim 20 wherein said mixture contains at least
45% by weight of said radiation inert liquid.
22. The method of claim 21 wherein said liquid aprotic polar
solvent includes heteroatoms capable of forming donor acceptor
bonds with alkali metal cations.
23. The method of claim 22 wherein said aprotic polar solvent is
selected from the group consisting of propylene carbonate,
gamma-butyrolactone, 1,3-dioxolane, and
2-methyltetrahydrofuran.
24. A method for forming an electrochemical cell comprising
assembling an anode half element and a cathode half element with a
radiation polymerizable electrolyte therebetween, said radiation
polymerizable electrolyte including a liquid radiation
polymerizable monomeric or prepolymeric, polyethylenically
unsaturated compound, a radiation inert ionically conducting
liquid, said ionically conducting liquid being an aprotic polar
solvent, and an ionizable alkali metal salt; and subjecting said
electrolyte to actinic radiation.
25. A radiation curable composition useful in forming a polymeric
network containing a liquid electrolyte, said composition
comprising a liquid, monomeric or prepolymeric, radiation
polymerizable polyethylenically unsaturated compound, a radiation
inert ionically conducting liquid, and an ionizable alkali metal
salt, said ionically conducting liquid being an aprotic polar
solvent.
26. The radiation curable composition of claim 25 wherein said
radiation polymerizable compound is a polyethylenically unsaturated
compound including at least one heteroatom in the molecule.
27. The radiation curable composition of claim 25 wherein said
liquid aprotic polar solvent includes heteroatoms capable of
forming donor acceptor bonds with alkali metal cations.
28. The radiation curable composition of claim 27 wherein said
aprotic polar solvent is selected from the group consisting of
propylene carbonate, gamma-butyrolactone, 1,3-dioxolane, and
2-methyl-tetrahydrofuran.
29. A method for forming a cathode half element which comprises
coating a metal foil with a mixture including an active cathode
material, an electronic conductor, a liquid monomeric or
prepolymeric, radiation polymerizable, polyethylenically
unsaturated compound, and a radiation inert ionically conducting
liquid, said ionically conducting liquid being a polar aprotic
solvent; and subjecting said mixture to radiation to thereby
crosslink said radiation polymerizable compound.
30. The method of claim 29 wherein said active cathode material is
an intercalation compound.
31. The method of claim 30 wherein said intercalation compound is a
vanadium oxide.
32. The method of claim 31 wherein said mixture additionally
includes an ionizable alkali metal salt.
33. The method of claim 32 wherein said radiation polymerizable
compound is an ethylenically unsaturated compound containing a
heteroatom.
34. A method for forming an electrochemical cell which comprises
coating an anodic metal foil member with a radiation polymerizable
electrolyte composition including a liquid, monomeric or
prepolymeric radiation polymerizable, polyethylenically unsaturated
compound, a radiation inert ionically conducting liquid, and an
ionizable alkali metal salt, said ionically conducting liquid being
a polar aprotic solvent; and overcoating said radiation
polymerizable electrolyte composition with a radiation
polymerizable cathode, composition including a liquid monomeric or
prepolymeric radiation polymerizable polyethylenically unsaturated
compound, an active cathode material, an electronic conductor, and
a radiation inert ionically conducting liquid.
35. The method of claim 34 wherein said method comprises the
additional steps of applying a metal foil current collector to the
surface of said radiation polymerizable cathode composition to form
an assembly, and subjecting said assembly to radiation.
36. The method of claim 34 wherein said method comprises the
additional steps of subjecting said electrolyte composition and
said cathode composition to radiation, and laminating a metal foil
current collector to the surface of said cathode composition.
37. A method for forming an electrochemical cell which comprises
coating a metal foil member with a radiation polymerizable cathode
composition including a liquid radiation polymerizable, monomeric
or prepolymeric, polyethylenically unsaturated compound containing
heteroatom, a radiation inert ionically conducting liquid, said
ionically conducting liquid being a polar aprotic solvent; an
active cathode material, and an electronic conductor; and
overcoating said radiation polymerizable cathode composition with a
radiation polymerizable electrolyte composition including a liquid
radiation polymerizable monomeric or prepolymeric polyethylenically
unsaturated compound, a radiation inert ionically conducting
liquid, and an ionizable alkali metal salt.
38. The method of claim 37 wherein said method comprises the
additional steps of laminating an anodic metal foil member to said
electrolyte composition to form an assembly, and subjecting said
assembly to radiation.
39. The method of claim 37 wherein said method comprises the
additional steps of subjecting said cathode composition and said
electrolyte composition to radiation, and laminating an anodic
metal foil member to the surface of said electrolyte
composition.
40. The method of claim 37 wherein said method comprises the
additional steps of applying an anodic metal foil member to the
surface of said electrolyte composition, and subjecting said
electrolyte composition to radiation to cure said electrolyte
composition.
41. The method of claim 37 comprising the additional steps of
subjecting said electrolyte composition to radiation to cure said
electrolyte composition, and laminating an anodic foil member to
the surface of said cured electrolyte composition.
42. A method for forming an electrochemical cell which comprises
coating an anodic metal foil member with a radiation polymerizable
electrolyte composition including a liquid, monomeric or
prepolymeric, radiation polymerizable, polyethylenically
unsaturated compound, a radiation inert ionically conducting
liquid, said ionically conducting liquid being a polar aprotic
solvent; and an ionizable alkali metal salt; subjecting said
electrolyte composition to radiation; and overcoating said cured
electrolyte composition with a radiation polymerizable cathode
composition including a liquid monomeric or prepolymeric radiation
polymerizable polyethylenically unsaturated compound, an active
cathode material, an electronic conductor, and a radiation inert
ionically conducting liquid.
43. The method of claim 42 comprising the additional steps of
laminating a metal foil current collector to the surface of said
cathode composition, and subjecting said cathode composition to
radiation to cure said cathode composition.
44. The method of claim 42 comprising the additional steps of
subjecting said cathode composition to radiation to cure said
cathode composition, and laminating a metal foil current collector
to the surface of said cured cathode composition.
45. A method for forming an electrochemical cell which comprises
coating an metal foil member with a radiation polymerizable cathode
composition including a liquid polymerizable, monomeric or
prepolymeric, polyethylenically unsaturated compound, a radiation
inert ionically conducting liquid, an active cathode material, and
an electronic conductor; subjecting said cathode composition to
radiation to cure said cathode composition; and overcoating said
cured cathode composition with a radiation polymerizable
electrolyte composition including a liquid radiation polymerizable
monomeric or prepolymeric polyethylenically unsaturated compound, a
radiation inert ionically conducting liquid, and an ionizable
alkali metal salt, said ionically conducting liquid being a polar
aprotic solvent.
46. A method for forming an electrochemical cell which comprises
coating an anodic metal foil member with a radiation polymerizable
electrolyte composition including a liquid, monomeric or
prepolymeric radiation polymerizable polyethylenically unsaturated
compound, a radiation inert ionically conducting liquid, and an
ionizable alkali metal salt; and coating a metal foil member with a
radiation polymerizable cathode composition including a liquid
radiation polymerizable monomeric prepolymeric polyethylenically
unsaturated compound a radiation inert ionically conducting liquid,
said ionically conducting liquid being a polar aprotic solvent; an
active cathode material and electronic conductor.
47. The method of claim 46 which further comprises the steps of
laminating said coated metal foil member with said coated anodic
member such that said electrolyte composition is in contact with
said cathode composition, and subjecting said electrolyte
composition and said cathodic composition to radiation to cure said
compositions.
48. The method of claim 46 comprising the additional step of
subjecting said cathode composition to radiation to cure said
composition, laminating said coated anodic metal foil member with
said said cathode composition such that said cured cathode
compositions contacts said electrolyte composition, and subjecting
said electrolyte composition to radiation to cure said electrolyte
composition.
49. The method of claim 46 which comprises the additional steps of
subjecting said electrolyte composition to radiation to cure said
electrolyte composition, laminating said coated metal foil member
with said cured electrolyte composition such that said cathode
composition contacts said cured electrolyte composition, and
subjecting said cathode composition to radiation to cure said
cathode composition.
50. The method of claim 46 wherein said method comprises the
additional steps of subjecting said electrolyte composition to
radiation to cure said electrolyte composition, subjecting said
cathode composition to radiation to cure said cathode composition,
and laminating said anodic metal foil member coated with said cured
electrolyte composition to said metal foil member coated with said
cured cathode composition such that said cured cathode composition
contacts said cured electrolyte composition.
Description
BACKGROUND OF THE INVENTION
The present invention relates to the manufacture of solid state
electrochemical devices and, more particularly, solid state
electrochemical devices in which the electrolyte is a polymeric
network interpenetrated by an ionically conducting liquid
phase.
Solid state electrochemical devices are the subject of intense
investigation and development. They are described extensively in
the patent literature. See, for example, U.S. Pat. Nos. 4,303,748
to Armand; 4,589,197 to North; 4,547,440 to Hooper et al. and
4,228,226 to Christiansen. These cells are typically constructed of
an alkali metal foil anode, an ionically conducting polymeric
electrolyte containing an ionizable alkali metal salt, and a finely
divided transition metal oxide as a cathode.
Bauer et al., U.S. Pat. No. 4,654,279, describes a cell in which
the electrolyte is a two phase interpenetrating network of a
mechanically supporting phase of a continuous network of a
crosslinked polymer and an interpenetrating conducting liquid
polymer phase comprising an alkali metal salt of a complexing
liquid polymer which provides continuous paths of high conductivity
throughout the matrix. In one embodiment, a liquid complex of a
lithium salt and polyethylene oxide is supported by an epoxy, a
polymethacrylate, or a polyacrylonitrile matrix.
The network is formed by preparing a solution of the metal salt,
the salt-complexing liquid polymer, and the monomer for the
crosslinked supporting phase in a polar solvent. The solvent is
evaporated to form a dry layer of a mixture of the remaining
materials. The dry layer is then cured.
Le Mehaute et al., U.S. Pat. No. 4,556,614, discloses a solid
electrolyte for an electrochemical cell in which a salt complexing
polymer is mixed with a miscible and crosslinkable second polymer.
The function of the second polymer is to maintain the complexing
polymer in a more highly conductive amorphous state. This is
accomplished by forming a solution of the two polymers and an
ionizable salt in a solvent, evaporating the solvent, and
crosslinking the second polymer. The second polymer is crosslinked
by radiation.
Andre et al., U.S. Pat. No. 4,357,601, generally relates to
crosslinked polymeric electrolytes containing heteroatoms. The
compositions described in the patent are chemically crosslinked,
for example, through the reaction of a polyol and a
polyisocyanate.
Xia et al., "Conductivities of Solid Polymer Electrolyte Complexes
of Alkali Salts with Polymers of Methoxypolyethyleneglycol
Methacrylates," Solid State Ionics, 14, (1984) 221-24 discloses
solid polymeric electrolytes of ionizable salts and polymers
prepared by polymerizing oligo-oxyethyl methacrylates. Reference is
made at the end of the paper to experiments with radiation
cross-linking. The polymers ranged from 150,000 to 300,000 in
molecular weight.
SUMMARY OF THE INVENTION
A principal object of the present invention is to provide a method
for forming a polymeric electrolyte for use in solid state
electrochemical cells and, more particularly, to provide a method
for manufacturing the anode and/or cathode half elements of such
cells or the cells themselves; and to provide electrolytes, anode
and cathode half elements and electrochemical cells formed by such
a method.
In accordance with the present invention the electrolyte is formed
by preparing a mixture of a liquid monomeric or prepolymeric
radiation polymerizable compound, a radiation inert ionically
conducting liquid, and an ionizable alkali metal salt, and curing
the mixture by exposing it to actinic radiation. In accordance with
the preferred embodiments of the invention, the mixture is cured by
exposure to ultraviolet or electron beam radiation. Where
ultraviolet radiation is used, the mixture will additionally
include an ultraviolet initiator.
The radiation polymerizable electrolyte composition may be coated
upon a support or placed in a mold prior to exposure. Exposure of
the mixture produces a polymerized or crosslinked (where
trifunctional monomers are used) matrix which is interpenetrated by
the radiation inert ionically conducting liquid phase. In
accordance with the most typical embodiments of the invention, the
radiation polymerizable compounds are preferably low molecular
weight polyethylenically unsaturated compounds and still more
preferably compounds having at least one heteroatom in the molecule
which is capable of forming donor acceptor bonds with an alkali
metal cation and having at least two terminal polymerizable
ethylenically unsaturated moieties. When polymerized, these
compounds form an ionically conductive matrix. The radiation inert
liquid is preferably a polar aprotic solvent or a solvent having
heteroatoms capable of forming donor acceptor bonds with alkali
metal cations such as polyethylene glycol dimethyl ether.
The method of the present invention can be used to manufacture
anode and cathode half elements as well as electrochemical cells.
Anode half elements are prepared by coating the radiation
polymerizable electrolyte composition described above on an
appropriate anodic material such as lithium metal on nickel or
copper foil; and conveying the coated foil member past a radiation
source. After exposure, the foil emerges with the ion conductive
network adhered to its surface. This not only provides intimate
contact between the foil and the electrolyte but it also protects
the underlying foil surface from damage during subsequent
manufacturing operations in which it is assembled with the cathode
element.
In accordance with one method of the present invention, a method
for providing a cathode hlf element is provided. In this method, a
mixture of an active cathode material, an electronic conductor, a
liquid monomeric or prepolymeric radiation polymerizable
polyethylenically unsaturated compound, a radiation inert ionically
conducting liquid, and optionally an ionizable alkali metal salt is
prepared; this mixture is coated on a foil member which functions
as a current collector, and exposed to actinic radiation to
polymerize the polyethylenically unsaturated compound. In some
cases the ionizable alkali metal salt may be omitted from the
radiation polymerizable cathode composition to facilitate coating.
An excess of an ionically conductive salt may be incorporated in
the electrolyte layer which subsequently diffuses into the cathode
layer when the cell is assembled.
The present invention is also useful in manufacturing a completed
electrochemical cell. In accordance with one method, anode and
cathode half elements prepared by any process may be assembled with
a layer of a radiation polymerizable electrolyte composition in
accordance with the present invention therebetween, and the
assembly may be exposed to radiation to cure the electrolyte layer
and thereby adhere to anode and cathode half elements together.
Other methods may also be used. For example, cured anode and
cathode half elements prepared in accordance with the present
invention may be assembled using heat and pressure in a
conventional manner. Alternatively, a cured anode or cathode half
element prepared by any process may be assembled with an uncured
anode or cathode half element in accordance with the present
invention and the assembly may be exposed to radiation to adhere
the two elements together. In accordance with still another method
of the present invention, uncured anode and cathode half elements
carrying radiation polymerizable compositions in accordance with
the present invention may be assembled and the assembly may be
exposed to radiation to cure the elements and at the same time
secure the cell together. It will also be apparent that a foil
member may be coated with a radiation polymerizable electrolyte and
cathode compositions in accordance with the present invention,
assembled with the foil member forming the anode or the current
collector for the cathode, and this assembly may be cured.
Accordingly, one manifestation of the present invention is a method
for forming an interpenetrating polymeric network containing a
liquid electrolyte for use in solid state electrochemical cells
which comprises forming a mixture of a liquid, monomeric or
prepolymeric radiation polymerizable compound, a radiation inert
ionically conducting liquid, and an ionizable alkali metal salt;
subjecting said mixture to actinic radiation to thereby crosslink
said radiation polymerizable compound and thereby form a solid
matrix containing said ionically conducting liquid.
Another manifestation of the present invention is a method for
forming an anode half element which comprises coating an anodic
metal foil member with a mixture which includes the aforementioned
radiation polymerizable material, a radiation inert ionically
conducting liquid, and an ionizable alkali metal salt; and
subjecting said mixture to actinic radiation to thereby crosslink
said radiation polymerizable compound and form a solid matrix
containing said ionically conducting liquid.
The present invention also provides a method for forming a cathode
half element which comprises forming a mixture of an active cathode
material, an electronic conductor, a liquid monomeric or
prepolymeric radiation polymerizable compound, a radiation inert
ionically conducting liquid, and optionally, an ionizable alkali
metal salt; coating said mixture on a metal foil member; and
exposing said mixture to radiation to cure said radiation
polymerizable polyethylenically unsaturated compound and thereby
form a polymeric network interpenetrated by said ionically
conducting liquid.
A further method in accordance with the present invention is a
method for forming an electrochemical cell which comprises
assembling an anode and a cathode half element having a radiation
polymerizable electrolyte composition therebetween including a
liquid monomeric or prepolymeric radiation polymerizable compound,
a radiation inert ionically conducting liquid, and an ionizable
alkali metal salt; and exposing the assembly to radiation to
polymerize the radiation polymerizable compound and thereby secure
the anode and cathode half elements together via a polymeric
network interpenetrated by said ionically conducting liquid.
Still another method in accordance with the present invention
comprises coating an anodic metal foil member with a radiation
polymerizable electrolyte composition including a liquid monomeric
or prepolymeric radiation polymerizable compound, a radiation inert
ionically conducting liquid, and an ionizable alkali metal salt;
overcoating said radiation polymerizable electrolyte composition
with a radiation polymerizable cathode composition including an
active cathode material, an electronic conductor, a liquid
monomeric or prepolymeric radiation polymerizable compound, a
radiation inert ionically conducting liquid, and optionally an
ionizable alkali metal salt; overlaying said radiation
polymerizable cathode composition with a foil member functioning as
a current collector for said cathode, and exposing the laminate so
obtained to radiation to polymerize the radiation polymerizable
compound and thereby form an electrochemical cell. This process may
be reversed in accordance with which the current collector for the
cathode may be coated with a radiation polymerizable cathode
composition which is overcoated with the radiation polymerizable
electrolyte composition described above. This material is assembled
with an anodic metal foil member and exposed to radiation.
DETAILED DESCRIPTION OF THE INVENTION
The network which is interpenetrated by the ionically conducting
liquid in the present invention may be a conductive matrix in which
case it is formed from monomers containing heteroatoms capable of
forming donor acceptor bonds with an alkali metal cation; or a
non-conductive supportive matrix in which case the aforesaid
heteroatoms are not present. The preferred monomers or prepolymers
are described below.
Polyethylenically unsaturated monomeric or prepolymonomeric
materials useful in the present invention are preferably compounds
having at least one, and more preferably a plurality, of
heteroatoms (particularly oxygen and/or nitrogen atoms) capable of
forming donor acceptor bonds with an alkali metal cation and are
terminated by radiation polymerizable moieties. These compounds
yield a conductive supportive matrix. More specifically they are
preferably low molecular weight oligomers of the formulae (I)-(III)
below ##STR1## where n is about 3 to 50 and R is hydrogen or a
C1-C3 alkyl group, which are terminated by ethylenically
unsaturated moieties or glycidyl moieties represented by A.
A particularly useful group of radiation polymerizable compounds is
obtained by reacting a polyethylene glycol with acrylic or
methacrylic acid. Also useful in the present invention are
radiation curable materials such as acrylated epoxies, e.g.,
Bisphenol A epoxy diacrylate, polyester acrylates, an acrylated
functionalized polyurethane such as Uvithan ZL-1178 available from
Morton Thiokol Chemical Company copolymers of glycidyl ethers and
acrylates or a vinyl compound such as N-vinylpyrrolidone. The
latter provides a non-conductive matrix. In selecting these
monomers, monomers are selected which do not adversely react with
the anodic metal which tends to be highly reactive. For example,
halogenated monomers such as vinyl chloride are preferably avoided.
Monomers which react with the anodic metal, but which react with it
very slowly may be used, but are not desirable.
Preferably, the radiation polymerizable polyethylenically
unsaturated compounds have a molecular weight of about 200 to 2,000
and more preferably 200 to 800. Still more preferably they are
liquids at temperatures less than 30.degree. C. Examples of
radiation curable materials include polyethylene glycol-300
diacrylate (average PEO molecular weight about 300), polyethylene
glycol-480 diacrylate (average PEO molecular weight about 480) and
the corresponding methacrylates.
It may be desirable to include a radiation curable comonomer in the
composition to reduce the glass transition temperature and improve
conductivity of the polymer. Any suitable monoacrylate such as
tetrahydrofurfuryl acrylate, tetrahydrofurfuryl methacrylate,
methoxypolyethylene glycol monomethacrylate, 2-ethoxyethyl
acrylate, 2-methoxyethyl acrylate or cyclohexyl methacrylate may be
used for this purpose. Triacrylates such as TMPTA,
trimethylolpropane ethoxylated triacrylate (TMPEOTA) or
trimethylolpropane propoxy triacrylate may be used to introduce
crosslinking of the polymer. There should be sufficient rigidity in
the layers maintaining separation of the anode and cathode that the
cell does not discharge with handling. Monoacrylates may be used in
an amount of about 5 to 50% by weight based on the total amount of
radiation polymerizable material. The triacrylates are used in
amounts of about 2 to 30% by weight on the same basis.
The supportive matrix may be formed in whole or in part from the
radiation curable compound. As illustrated in Examples 12 and 13
amounts of higher molecular weight PEO may be added to the
composition.
The radiation inert liquids which form the ionically conductive
liquid interpenetrating phase can be any low volatile aprotic polar
solvent. Preferably, these materials are characterized by a boiling
point greater than about 80.degree. C. Representative examples are
propylene carbonate, .gamma.-butryrolactone, 1,3-dioxolane, and
2-methyltetrahydrofuran. Less polar solvents having heteroatoms
capable of bonding alkali metal cations are also useful. Low
volatility simplifies manufacture and improves shelf life.
Polyethylene glycol dimethyl ether (PEGDME) is a preferred example.
Glymes such as tetraglyme, hexaglyme, and heptaglyme are also
desirable solvents.
The radiation curable mixture of this invention contains at least
45% by weight of the radiation inert liquid and about 20 to 55% by
weight and preferably 25 to 40% by weight of the radiation
polymerizable compound. The exact amount of the radiation
polymerizable compound and the radiation inert liquid should be
adjusted to provide the optimum combination of strength and
conductivity for the particular application. As a general rule, if
the mixture contains less than about 20% of the polymerizable
compound, the electrolyte will be too weak to maintain electrode
separation. If the mixture contains greater than about 55%
polymerizable material, the electrolyte exhibits poor conductivity.
In those cases in which the electrolyte composition itself or an
electrode composition containing the electrolyte is coated on a
supporting member, such as a current collector or an electrode half
element, the electrolyte often is not required to have the
structural integrity of a free standing film. In those applications
it is permissible and advantageous to use a higher quantity of the
radiation inert liquid because greater conductivity can be
achieved, for example it is advantageous to use about 70 to 80% of
the radiation inert liquid.
Ionizable alkaline metal salts useful in this invention include
those salts conventionally used in solid state electrochemical
cells. Representative examples are sodium, lithium, and ammonium
salts of less mobile anions of weak bases having a large anionic
radius. Examples may be selected from the group consisting of
I.sup.-, Br.sup.-, SCN.sup.-, ClO.sub.4.sup.-, BF.sub.4.sup.-,
PF.sub.6.sup.-, AsF.sub.6.sup.-, CF.sub.3 COO.sup.-, CF.sub.3
SO.sub.3.sup.-, etc. Specific examples are LiClO.sub.4,
NaClO.sub.4, LiF.sub.3 CSO.sub.3, and LiBF.sub.4.
The salt may be used up to an amount which does not exceed its
solubility limit in the electrolyte. The amount will therefore vary
with the nature of the radiation polymerizable material and the
radiation inert liquid solvent. As a general rule, the maximum
amount of salt within its solubility limit should be used to
maximize the ionic conductivity of the electrolyte. In most
applications about 10 to 60 parts salt is used per 100 parts of
radiation inert liquid phase.
The method of the present invention can be used to produce free
standing films or electrode half elements. To produce a free
standing film, the radiation curable mixture may be poured into a
mold or coated onto a surface having a release characteristic such
as PTFE and cured by exposure to actinic radiation. The electrolyte
film thickness can vary but films about 15 to 100 microns thick and
preferably 20 to 50 microns thick are useful in many applications.
The obtained film can be assembled with cathode and anode half
elements prepared by the processes disclosed herein or prepared by
other processes and laminated under heat and pressure. A conductive
adhesive may be used if necessary.
Anode half elements are obtained by coating a foil of the anode
metal with the radiation curable composition and exposing to
radiation. A typical foil is lithium foil or lithium coated foil
such as nickel or copper foil having a layer of lithium deposited
on its surface. Lithium is preferred because it is very
electropositive and light in weight. The radiation curable
composition may be coated in any manner. Suitable techniques are
rod coating, roll coating, blade coating, etc.
Coating compositions for cathode half elements include particles of
the insertion compound and an electrically conductive material. The
cathode half element is obtained by coating a foil member such as
nickel foil with the aforesaid composition in a thickness of about
10 to 100 microns and preferably about 30 to 60 microns, and
curing. The cathode composition may be coated by any of the
techniques discussed previously, but it is particularly desirable
to design an extrudable cathode composition. The radiation curable
composition used in the present invention functions as a dispersing
medium for the cathode materials. A typical coating formulation for
a cathode half element may contain about 50 to 80 parts of the
insertion compound, about 2 to 15 parts of a conductive particle
such as carbon black and about 15 to 50 parts of the radiation
curable composition described above. As previously indicated the
ionizable salt can be omitted from the cathode composition if it is
able to diffuse into the cathodes after assembly with the
electrolyte. It may enhance the extrudability of the cathode
composition to omit the salt and rely upon its diffusion within the
electrochemical cell to fill the cathode. Also, for extrudability,
it may be desirable to use a higher amount of ionically conductive
liquid in the cathode composition and less in the electrolyte
composition and to rely upon diffusion to balance the concentration
when the cell is formed.
Insertion compounds and electronically conductive materials useful
in the present invention are well known in the art. Representative
examples of insertion compounds are V.sub.6 O.sub.13, MoO.sub.2,
MnO.sub.2 and TiS.sub.2. Other examples can be found in the
aforementioned references. A conductive material is carbon black.
Certain conductive polymers (which are characterized by a
conjugated network of double bonds) like polypyrol and
polyacetylene may also be used for this purpose.
In accordance with a further embodiment of the invention, the
composite cathodic particles described in U.S. Pat. No. 4,576,883
to Hope can be dispersed in the curable composition and coated on a
metal foil member as described above.
In preparing the coating compositions for the cathode half element,
a small amount of a volatile solvent and a dispersing agent such as
lecithin can be added to disperse the cathodic material in the
composition and produce a composition having good coating
characteristics.
The term "actinic radiation" as used herein includes the entire
electromagnetic spectrum and electron beam and gamma radiation. It
is anticipated, however, based on availability of radiation sources
and simplicity of equipment that electron beam and ultraviolet
radiation will be used most often. Electron beam and gamma
radiation are advantageous because they do not require the presence
of a photoinitiator. When a photoinitiator is required, for example
when using ultraviolet radiation, initiators selected from among
conventional photoinitiators may be used. When using electron beam,
the beam potential must be sufficiently high to penetrate the
electrode layer, the anode or cathode half element, or the cell
itself depending upon which manufacturing technique is adopted.
Voltages of 175 to 300 KV are generally useful. The beam dosage and
the speed with which the element traverses the beam are adjusted to
control the degree of crosslinking in an otherwise known
manner.
It will be apparent from the foregoing description that the methods
of the present invention can also be used to manufacture a complete
electrochemical cell. Cured anode and cathode half elements
prepared as above can be laminated together under heat and pressure
in an otherwise known manner. Alternatively, however, the
electrochemical device can be assembled "wet" and then cured in
situ. For example, in accordance with the present invention, a
lithium coated foil member can be coated with the radiation
polymerizable electrolyte composition and overcoated with the
cathode coating composition described previously; or a nickel foil
member can be coated with the cathode coating composition described
previously and overcoated with the radiation polymerizable
electrolyte composition. These structures can be cured by exposure
to electron beam or another source of actinic radiation and the
current collector or anodic member can be assembled with it. In
another embodiment the foil members associated with both the anode
and the cathode half elements may be assembled to form the
completed cell and this structure may be cured by electron beam as
shown in Example 11.
Thus, in one method a current collector such as a nickel foil
member may be coated with a radiation polymerizable cathode
composition in accordance with the present invention. This
structure is overcoated with a layer of the radiation polymerizable
electrolyte composition described above and assembled with an
anodic member such as a lithium foil member or a lithium coated
nickel or aluminum member. This assembly may be cured by exposure
to electron beam to provide an electrochemical cell. The cured
electrolyte and cathode compositions adhere to one another as well
as to the metal foil members associated with the anode and
cathode.
The process described above can also be reversed. An anodic metal
foil member such as lithium coated metal foil can be coated with
the radiation polymerizable electrolyte composition described
above. The radiation polymerizable cathode composition is coated
over the electrolyte composition and a nickel foil member or other
current collector is applied to the cathode layer. The assembly is
subjected to electron beam radiation to produce an electrochemical
cell in accordance with the present invention.
In another process, the anodic foil member or the current collector
may be coated with the appropriate cathode or electrolyte
composition and that composition may be cured (e.g., by exposure to
radiation when it is radiation curable). The cured composition may
be overcoated with the other of the electrolyte or cathode
composition thereafter, and the overcoating may be cured or the
remaining anodic foil member or current collector may be laminated
and then the overcoating cured.
Other methods for manufacturing anodes, cathodes, or
electrochemical cells will also be evident which utilize the
radiation polymerizable electrolyte composition of the present
invention. It has been found that this composition is effective in
bonding the anode and cathode elements together and, at the same
time, provides a polymeric matrix interpenetrated by an ionically
conductive liquid.
The invention is illustrated in more detail by way of the following
non-limiting examples.
EXAMPLE 1
1 g of poly(ethylene glycol) diacrylate, M.W. 300, 1 g of
poly(ethylene glycol) dimethyl ether, M.W. 400, and 0.3 g of
lithium trifluoromethane sulfonate were mixed together.
Benzophenone, 0.1 g was then added and the mixture, as a thin
layer, poured into an aluminum weighing dish. This mixture was
irradiated in an Argon atmosphere for 1 minute with GE F40/BLB
blacklight, (output range from 300-420 nm and output maximum
slightly above 350 nm). The exposure transformed the liquid mixture
into a flexible, opaque film with a dry feel. Its ionic
conductivity is 2.8.times.10.sup.-5 ohm.sup.-1 cm.sup.-1.
EXAMPLE 2
0.5 g of poly(ethylene glycol) diacrylate, 0.5 g of poly(ethylene
glycol) diglycidyl ether, 1 g of poly(ethylene glycol) dimethyl
ether and 0.6 g of lithium trifluoromethane sulfonate were mixed
together, 0.1 g of benzophenone was then added and then the mixture
irradiated in an aluminum weighing dish, using the same U.V. lamp
as in Example 1. The flexible, opaque film had an ionic
conductivity of 2.7.times.10.sup.-5 ohm.sup.-1 cm.sup.-1.
EXAMPLE 3
2 g of poly(ethylene glycol)diacrylate, avg. M.W. 300, 2 g of
poly(ethylene glycol)dimethyl ether, avg. M.W. 400, and 0.6 g of
lithium trifluoromethane sulfonate were mixed together. This
mixture was then coated on aluminum foil and irradiated by electron
beam with 3 Megarads at 20 ft/min. (Energy Science Inc.). This
resulted in a clear and flexible dry film.
EXAMPLE 4
2 g of UVITHANE ZL-1178. 2 g of poly(ethylene glycol)dimethylether
and 0.6 g of lithium trifluoromethane sulfonate were mixed
together. UVITHANE ZL-1178 is a diacrylate functionalized
polyurethane with ether portions built up from poly(propylene
glycol) from Morton Thiokol Chemical Co. This mixture was then
coated on aluminum foil and irradiated by electron beam with 3, 6,
9 and 12 MR (Megarads) at 20 ft/min. (fpm). This resulted in clear
and flexible dry films.
EXAMPLE 5
Onto a sheet of industrial strength aluminum foil was coated with a
drawdown bar a film of the following mixture:
______________________________________ Poly(ethylene
glycol)diacrylate 2.0 g (avg. M.W. of PEO 300) Poly(ethylene
glycol) dimethyl ether 2.0 g (avg. M.W. of PEO 400) Lithium
trifluoromethane sulfonate 0.6 g
______________________________________
The coated foil was passed through the path of an electron beam
emitting source at a speed of 20 fpm. Doses of 3, 6, 9, and 12 MR
were used. In all four cases a polymer film cured onto the aluminum
foil was obtained. The resulting ionic conductivities on the order
of 10.sup.-5 (ohm cm.sup.-1).
EXAMPLE 6
Onto a sheet of industrial strength aluminum foil was coated with a
drawdown bar a film of the following mixture:
______________________________________ Poly(ethylene
glycol)diacrylate 2.0 g (avg. M.W. of PEO 300) Poly(ethylene
glycol) dimethyl ether 1.0 g (avg. M.W. of PEO 400) Lithium
trifluoromethane sulfonate 0.1 g Unitized V.sub.6 O.sub.13
particles 1.0 g [70% V.sub.6 O.sub.13, 20% PEO (M.W. 400,000) 10%
Shawinigan carbon prepared as described in U.S. Pat. No. 4,576,883]
______________________________________
The coated aluminum foil was passed through the path of an electron
beam emitting source at a speed of 20 fpm and dosage of 12 MR. A
black flexible polymer film on an aluminum was the result.
EXAMPLE 7
Onto a sheet of industrial strength aluminum foil was coated with a
drawdown bar a film of the following mixture:
______________________________________ Poly(ethylene
glycol)diacrylate 2.5 g (avg. M.W. of PEO 300) Poly(ethylene
glycol) dimethyl ether 2.8 g (avg. M.W. of PEO 400) Uvithane
ZL-1178 2.8 g Lithium trifluoromethane sulfonate 0.84 g Unitized
V.sub.6 O.sub.13 3.0 g ______________________________________
The coated foil was passed through the path of an electron beam
source at a speed of 20 fpm and a dose of 12 MR. This resulted in
curing the liquid film into a flexible black polymer on aluminum
foil.
EXAMPLE 8
Onto a sheet of industrial strength aluminum foil was coated with a
drawdown bar a film of the following mixture which had been ground
in a ball mill to the desired particle size.
______________________________________ V.sub.6 O.sub.13 35 g
Lecithin 0.75 g Methylethyl ketone (MEK) 33 g Heptaglyme 15 g
Carbon black 3.5 g Polyethylene Glycol Diacrylate 15. g
______________________________________
The solvent (MEK) was allowed to evaporate. The resulting film was
then passed through the path of an electron beam source at a speed
of 50 fpm and a dose of 12 Megarads. This gave a cured flexible
black film useful as a cathode half element.
EXAMPLE 9
A film was prepared as in Example 8 without curing. A mixture of
pre-polymer electrolyte as in Example 5 was then coated on top of
it. This sample was then passed through the path of an electron
beam source at a speed of 50 fpm and a dose of 12 MR. This gave a
cured, glossy black film which could be assembled with another foil
member for use as an electrochemical device.
EXAMPLE 10
A coating was prepared and cured as in Example 8. A mixture of
pre-polymer electrolyte as in Example 5 was then coated on top of
it. This sample was then passed through electron beam source at a
speed of 50 fpm and a dose of 3 MR. This gave a cured black film
which could be assembled with another foil member for use as an
electrochemical device.
EXAMPLE 11
The coatings were prepared as described in Example 9. The coatings
were then covered with nickel foil. This construction was then
cured by passage through an electron beam operating at 175 KV, a
dosage of 6 MR and a speed of 20 fpm to provide an electrochemical
device. Nickel foil was selected merely to demonstrate that the
electrode and electrolyte compositions could be cured by electron
beam through the foil. To prepare an electrochemical cell, the
cathode composition of Example 8 would be coated on a lithium foil
member or a lithium coated member in a dry room.
EXAMPLE 12
The radiation curable extrudable polymer electrolyte compositions
containing polyethylene oxide (PEO), polyethylene glycol
diacrylate, (PEG-DA), trimethylolpropane ethoxylated triacrylate
(TMPEOTA), LiCF.sub.3 SO.sub.3 and a suitable ionic conductive
solvent such as tetraglyme or propylene carbonate were made and
extruded on aluminum foil using a Brabender extruder at 125.degree.
C. as shown in the Table below. The extrusion mixture was prepared
as follows: First, the salt was dissolved in half of the propylene
carbonate. The PEO is dispersed in the other half of the propylene
carbonate, then PEG-DA and TMPEOTA are added to the mixture. The
salt and the PEO compositions are mixed and the mixture is poured
into the input of the extruder.
TABLE ______________________________________ Sample No. (wt. %)
Compound 1 2 3 4 ______________________________________ PEG-DA
(400) -- -- 0.04 0.10 TMPEOTA 0.03 0.13 0.01 0.01 Tetraglyme 0.70
0.60 0.75 0.65 PEO 0.20 0.20 0.05 0.10 LiCF.sub.3 SO.sub.3 0.07
0.07 0.15 0.14 ______________________________________
Samples 1-4 were then passed through the electron beam at 7.8 MR to
give flexible, opaque films about 1 to 5 mils thick having a
conductivity of 7.times.10.sup.-5 ohm.sup.-1 cm.sup.-1.
EXAMPLE 13
The following mixtures containing propylene carbonate (PC) were
also made:
______________________________________ Sample No. (wt. %) Compound
PC-1 PC-2 ______________________________________ PEG-DA 0.10 0.10
TMPEOTA 0.01 0.01 PC 0.65 0.65 PEO 0.10 0.05 LICF.sub.3 SO.sub.3
0.14 0.19 ______________________________________
The materials were extruded under the same conditions described in
Example 12 and passed through the electron beam to give clear,
flexible films having a conductivity of 2.times.10.sup.-3
ohm.sup.-1 cm.sup.-1.
EXAMPLE 14
Cathode mixtures containing 50% V.sub.6 O.sub.13, 7% Shawinigan
Black and 43% of compositions PC-1 and PC-2 from Example 13 were
extruded onto nickle or aluminum foil under the same conditions as
described above and cured by electron beam at 7.8 MR.
EXAMPLE 15
Batteries were made as follows:
(1) Extruding the cathode composition of Example 14 on aluminum
foil;
(2) Curing the cathode composition by electron beam as in Example
14;
(3) Extruding composition PC-2 from Example 13 on top of the cured
cathode composition;
(4) Laminate with lithium foil;
(5) Passing the structure through an electron beam at 7.8 MR. The
lithium foil retained its property during this process.
EXAMPLE 16
Batteries were made as follows:
(1) Extruding the cathode composition of Example 14 on aluminum
foil;
(2) Curing the cathode composition by electron beam as in Example
14;
(3) Extruding composition PC-2 from Example 13 on top of the cured
cathode composition;
(4) Passing the coating through the electron beam at 7.8 MR;
(5) Laminating lithium foil to the laminate of step (4) by heat
and/or pressure roll.
Having described the invention in detail and by reference to
preferred embodiments thereof, it will be apparent that
modifications and variations are possible without departing from
the scope of the appended claims.
* * * * *